PHOTOCHEMICAL-SYNTHESIS AND REACTIONS OF FEH(C6H4PPHCH2CH2PPH2) (PPH2CH2CH2PPH2)
PHOTOCHEMICAL-SYNTHESIS AND REACTIONS OF FEH(C6H4PPHCH2CH2PPH2) (PPH2CH2CH2PPH2)
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DOI：
10.1021/ic00143a002
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发表时间：
1983-01-01
影响因子：
4.6
通讯作者：
MORRIS, RH
中科院分区：
文献类型：
--
作者：
AZIZIAN, H;MORRIS, RH
图1. 31P| 'H| NMR光谱参考插入管中C6 D 6中的5% P（OCH 3）3（139.8 ppm处的峰）：（a）FeH 2（DPPE）2在苯中的溶液;（B）在用N2吹扫的UV照射60分钟后获得的2的溶液;（c）产物，络合物1，在H2吸收测量为0.97 mol/mol Fe后（在处理样品时发生少量氧化（峰在17.8 ppm））。表示化合物1和2的50：50混合物。该膜在25 ℃下与一氧化碳（1atm）反应1h，得到Fe（CO）（DPPE）2，v（CO）= 1834 cm-1和Fe（CO）3（DPPE），v（CO）= 1978、1935、1910 cm-1的混合物（在Nujol中）。5 FeH 2（N2）（PPh 2 Et）3的固态光解。通过上述方法B在烧瓶上沉积黄色固体的薄膜。在可见光照射2分钟后，收集0.28摩尔气体/摩尔铁，并通过GC分析为70%N2和30%H2。2.5小时后，放出0.8摩尔气体（75%N2，25%H2）。通过连续照射，可以获得1.4摩尔气体/摩尔铁。棕色空气敏感性产物在Nujol中的IR光谱显示出由于起始络合物y（NN）= 2055 cm-1、v（FeH）= 1850 cm-1、游离膦v（CH）= 1590 cm-1和邻位金属化膦r（CH）= 1538 cm-1而产生的谱带。该固体与一氧化碳反应24小时，得到Fe（CO）3（PPh 2 Et）2，v（CO）= 1880，1860 cm-1，作为主要的含CO产物。14
Figure 1. 31P|‘H| NMR spectra referenced to 5% P (OCH3) 3 in C6D6 in an insert tube (peak at 139.8 ppm):(a) FeH2 (DPPE) 2 in benzene;(b) solution of 2 obtained after 60 min of UV irradiation with an N2 purge;(c) the product, complex 1, after the H2 uptake measurement of 0.97 mol/mol of Fe (asmall amount of oxidation occurred (peak at 17.8 ppm) while the sample was handled). indicated a 50: 50 mixture of compounds 1 and 2. Reaction of this Film at 25 C with carbon monoxide (1 atm) for 1 h gave a mixture of Fe (CO)(DPPE) 2, v (CO)= 1834 cm"* 1, and Fe (CO) 3 (DPPE), v (CO)= 1978, 1935, 1910 cm" 1 (in Nujol). 5 Solid-State Photolysis of FeH2 (N2)(PPh2Et) 3. A thin film of the yellow solid was deposited on a flask by method B above. After 2 min of visible irradiation, 0.28 mol of gas/mol of iron was collected and analyzed by GC as 70% N2 and 30% H2. After 2.5 h 0.8 mol of gas (75% N2, 25% H2) was evolved. By continued irradiation, 1.4 mol of gas/mol of iron could be obtained. The IR spectrum in Nujol of the brown air-sensitive product showed bands due to the starting complex y (NN)= 2055 cm" 1, v (FeH)= 1850 cm" 1, free phosphine v (CH)= 1590 cm" 1, and ortho-metalated phosphine r (CH)= 1538 cm" 1. This solid reacted with carbon monoxide over 24 h to give Fe (CO) 3 (PPh2Et) 2, v (CO)= 1880, 1860 cm" 1, as the major CO-containing product. 14